The present invention relates to a polymer and process for making the same, more particularly to a polythioether formed by a process of combining a polythiol, polyepoxide and a polyvinyl ether.
Thiol-terminated sulfur-containing polymers have a long history of use in aerospace sealants because of their fuel resistant nature upon cross-linking. Among the commercially available polymeric compounds having sufficient sulfur content to exhibit this desirable property are the polysulfide polymers described, e.g., in U.S. Pat. No. 2,466,963 and sold under the trade name LP(copyright) polysulfide by Morton International of Chicago, Ill., and the alkyl side chain containing polythioether polymers described, e.g., in U.S. Pat. No. 4,366,307 that are sold only in complete sealant formulations by PRC-DeSoto International, Inc. of Glendale, Calif. In addition to fuel resistance, polymers useful in this context must also have the desirable properties of low temperature flexibility, liquidity at room temperature, high temperature resistance, a reasonable cost of manufacture, and not be so malodorous as to prevent commercial acceptance of compositions that contain the subject polymers.
Air frame manufacturers are actively striving to increase productivity by using faster curing aerospace sealants. Hand mixing and application are still common in the aerospace industry owing to high production standards, and as such, an aerospace sealant formulation requires a relatively long application life. For example, prior art manganese dioxide cured polysulfide sealants had a two hour application life and required about a two day cure to attain a Shore A hardness of 30. Current aerospace sealants are expected to have an application life of two to three hours and obtain a Shore A hardness of 30 in less than eight hours.
Until now, aerospace sealants based upon these sulfur-containing polymers have been crosslinked by oxidation of the thiol terminal groups with metal oxides or peroxides. Optimum properties with regard to elasticity are obtained by curing with manganese dioxide. Unfortunately, such sealants, when continuously exposed to modem mercaptan containing aviation fuels, e.g., as in integral fuel tank sealing applications, exhibit polymer chain degradation as evidenced by a phenomena known as xe2x80x9cchalking.xe2x80x9d
Another disadvantage of these systems has only recently come to light. Aircraft manufacturers, in an effort to increase the fuel economy of their airplanes, have an active program in place to reduce the weight of components they use. Sealant manufacturers have responded to this request for lower density sealants by incorporating lightweight fillers. The disadvantage with this approach is that only a relatively small quantity of these fillers can be used without dramatically decreasing the sealant""s physical strength.
Only recently, the specific gravity of aerospace sealants has been reduced from the 1.6-1.8 range down to a minimum of approximately 1.0. Those skilled in the art have attained this specific gravity by incorporating fine hollow spheres and compensating for the loss in physical strength by additions of more highly reinforcing fillers and pigments such as precipitated calcium carbonate or fuimed silica. The flaw with this approach is that the more highly reinforcing fillers have higher surface areas and in most cases higher oil absorptions. This higher surface area results in increased pigment-polymer interactions resulting in a dramatically increased viscosity. These higher viscosities negatively impact application properties and adhesion.
A polythioether is provided of the formula 
wherein R1 is H, C1-6 alkyl, C1-6 alkyl alcohol, C1-6 alkyl substituted with at least one of: 
xe2x80x94NHR5 wherein R5 is a C1-6 alkyl, R2 is C2-6 alkyl, C6-8 cycloalkyl, C6-10 alkylcycloalkyl, xe2x80x94[xe2x80x94(CH2)rxe2x80x94Qxe2x80x94]sxe2x80x94(CH2)txe2x80x94, or C1-2 alkyl substituted forms thereof, wherein r is an integer value from 2 to 8, Q is a heteroatom selected from the group consisting of: O, S, xe2x80x94NHxe2x80x94 and xe2x80x94NCH3xe2x80x94, S is an integer value from 1 to 5, and t is an integer value from 2 to 10, R3 is H or C1-4 alkyl, R4 is xe2x80x94CH2xe2x80x94 or R2, M is a C1-10 alkyl, C6-20 aryl, C6-20 aryl substituted with at least one C1-8 alkyl group, or a N or O heteroatom, Y is C2-20 alkyl, C6-20 cycloalkyl, C6-10 alkylcycloalkyl, or xe2x80x94[xe2x80x94(CH2)rxe2x80x94Qxe2x80x94]sxe2x80x94(xe2x80x94CH2xe2x80x94)txe2x80x94, n is an integer value from 1 to 60, m is an integer value from 1 to 60, and p is an integer value from 1 to 10, wherein the polythioether has a viscosity at 20xc2x0 C. of less than 1000 poise. Preferably, the polythioether has a number average molecular weight between about 1000 and about 10,000 Daltons. A polyfunctionalizing agent is optionally provided in order to increase the functionality of a polythioether from 2 to 5 with the most preferred range being 2 to 3.
A process for forming such a polythioether includes the steps of reacting a polythiol with either an aromatic polyepoxide or a polyvinyl ether to form a prepolymer. The prepolymer is then combined with the other of the aromatic polyepoxide or the polyvinyl ether. The use of such a polythioether is contemplated as an aerospace sealant.
It has surprisingly been discovered that the combination of certain polythiols with polyepoxides and oxygenated dienes according to the invention results in polythioether polymers that are liquids at room temperature and pressure. Further, these new polythioether polymers are higher in strength than either conventional polysulfide or polythioether polymers. Despite the increase in physical strength, polymer formulations consistent with this invention do not sacrifice other desirable physical and chemical properties inherent with polythioether polymers. The polythioether polymers of the present invention are substantially free of both malodorous cyclic byproducts and deleterious catalyst residues, and hence have superior thermal resistance properties. The inventive polythioethers have utility as aerospace sealants.
According to the invention, the combination of polythiols with polyepoxides and oxygenated dienes may be represented as follows: 
Suitable polythiols include the dithiols wherein R2 is a C1-10 alkyl or aryl and may or may not contain a heteroatom. Substituents on R2 are those which do not interfere with the reaction of the polythiol with either a polyepoxide or polydiene. Thus, R2 is free of reactive unsaturated carbon to carbon bonds, as well as highly water sensitive species. Preferred heteroatoms are S and O. Preferred dithiols include straight chain aliphatic dithiols with a chain length of two to six carbon equivalents, dimercaptodiethylene (DMDE), dimercaptodiethylsulfide (DMDS), dimercaptodioxaoctane (DMDO), dipentene dimercaptan, and vinylcyclohexane dimercaptan. Additional operative dithiols are recited in U.S. Pat. No. 5,912,319.
Suitable polyepoxides include those wherein group M is a C2-10 alkyl, C6-20 aryl, C6-20 aryl substituted with at least one C1-8 alkyl group, or a N or O heteroatom. Suitable polyepoxide compounds operative herein are recited in U.S. Pat. No. 4,136,086. Preferably, polyepoxides according to the present invention contain an aryl group within M. It has been discovered that an aryl backbone component synergistically operates with the hydroxyl groups associated with thiol epoxide reaction to form a superior strength and handling property polythioether polymer. R3 of an inventive polyepoxide reagent is hydrogen or C1-C4 alkyl. Preferably, R3 is hydrogen or a methyl group. R4 is methylene or any of the substituents denoted as the polythiol R2. P is an integer value ranging from 1 to 10. Additionally operative polyepoxides include the diglycidylether of bisphenol A (such as EPON 828(copyright), Shell Chemicals Ltd.), diglycidylether of bisphenol F (such as ERISYS(trademark), CVC), any of the lower functionality Novolaks (such as DEN 431(trademark), The Dow Chemical Co.), as well as butane- and hexane-diol diglycidyl ether (such as ARALDITE(copyright), Ciba-Geigy).
Suitable polyvinyl ethers include those wherein group Y is C2-10 alkyl, C6-10 cycloalkyl, C6-10 alkyl cycloalkyl or xe2x80x94[xe2x80x94(CH2)rxe2x80x94Oxe2x80x94]sxe2x80x94(CH2)txe2x80x94, where r is an integer value between 1 and 8, s is an integer value between 1 and 5, and t is an integer value between 2 and 10. Preferred polyvinyl ethers include the divinylethers of ethylene glycol, butanediol, hexanediol, diethylene glycol, triethylene glycol and tetraethylene glycol. Additionally, a blend of two or more of these divinyl ethers are equally suitable and are within the scope of this invention. Commercial blends of divinyl ethers are available from BASF under the trade name PLURIOL(copyright) and from International Specialty Products under the product designation xe2x80x9cDPE.xe2x80x9d
In the representative reaction scheme illustrated above, the subscripts n and m are chosen such that the resulting polymer has a molecular weight, Tg, and room temperature viscosity within the requisite range, for example, of an aerospace sealant, and such that m greater than n. Preferred molecular weight includes 1000-6000 Daltons. In one embodiment, Tg should be as low as possible but below xe2x88x9240xc2x0 C. Finally, room temperature viscosity should be below 1000 poise.
In another embodiment, the inventive polythioether is greater than difunctional and is represented by the formula: Bxe2x80x94(I-R1)z where B is a z-valent residue of a polyfunctionalizing agent, z is an integer value from 3 to 6, I is the resulting polythioether of Formula I less the terminal hydrogen groups, and R1 is H, C1-6 alkylene, C1-6 alkyl alcohol, C1-6 alkyl substituted with at least one of: 
Preferably, the average functionality, as defined as the number of reactive groups per polythioether molecule, ranges between about 2.05 and about 3.00.
While in the first preferred embodiment of the present invention as summarized by Formula I, an excess of dithiol is present to assure thiol termination of the resulting polythioether polymer, it is appreciated that by varying the relative amounts of polythiol relative to polyepoxide or polyvinyl ether, that polymers can be prepared that have not only terminal thiol groups, but terminal vinyl or epoxide groups. Furthermore, the polythioether polymers thus formed need not be further reacted prior to cure or, alternatively, are further reacted with other compounds to form capped polythioether polymers. Capping of polythioethers of the present invention affords the opportunity to include additional terminal functionalities into the inventive polymers. Such capping moieties illustratively include hydroxyl groups, secondary amine groups and alkyl groups.
In aerospace sealant applications, the polythioether polymer derived according to the invention may be combined with suitable lightweight fillers. Typically, a polythioether polymer is present at from about 40 to about 80 weight percent, 0.3 to 1.5 weight percent lightweight fillers or 10 to 50 weight percent of conventional inorganic fillers, 0.1 to 2 weight percent curing agent, and the remainder of the composition optionally including one or more additives of: pigments, cure accelerators, surfactants, adhesion promoters, thixotropic agents and solvents. Suitable lightweight fillers for use in this invention may be organic, inorganic, or a composite of both. They fall within two categoriesxe2x80x94microspheres and amorphous fillers. The amounts of the microspheres and amorphous lightweight fillers used in the composition of the invention may be from about 0.3 to about 10 percent and from about 4 to 15 percent of the total weight of the composition, respectively. The specific gravity (s.g.) of the microspheres ranges from about 0.1 to 0.7 and are exemplified by polystyrene foam, microspheres of polyacrylates and polyolefins, and silica microspheres having particle sizes ranging from 5 to 100 microns and a specific gravity of 0.25 (ECCOSPHERES(copyright), W. R. Grace and Co.). Other examples include alumina/silica microspheres having particle sizes in the range of 5 to 300 microns and a specific gravity of 0.7 (FILLITE(copyright), Pluess-Stauffer International), aluminum silicate microspheres having a specific gravity of from about 0.45 to about 0.7 (Z-LIGHT(copyright)), and calcium carbonate-coated polyvinylidene copolymer microspheres having a specific gravity of 0.13 (DUALITE 6001AE(copyright), Pierce and Stevens Corp.).
Suitable amorphous lightweight fillers for use in this invention have a specific gravity ranging from about 1.0 to about 2.2 and are exemplified by calcium silicates, fumed silica, precipitated silica, and polyethylene. Examples include calcium silicate having a specific gravity of from 2.1 to 2.2 and a particle size of from 3 to 4 microns (HUBERSORB HS-600(copyright), J. M. Huber Corp.) and fumed silica having a specific gravity of 1.7 to 1.8 with a particle size less than 1 (CAB-O-SIL TS-720(copyright), Cabot Corp.). Other examples include precipitated silica having a specific gravity of from 2 to 2.1 (HI-SIL TS-7000(copyright), PPG Industries), and polyethylene having a specific gravity of from 1 to 1.1 and a particle size of from 10 to 20 microns (SHAMROCK S-395(copyright), Shamrock Technologies Inc.).